The 2ν3 Raman overtone of sulfur hexafluoride: Absolute spectra, pressure effects, and polarizability properties

Abstract

Of the six normal vibrations of SF6, ν3 has a key role in the mechanisms of radiative forcing. This vibration, though inactive in Raman, shows up through the transition 2ν3 allowing for a complementary view on the asymmetric stretch of the molecule. Here, we look back into this topic, which has already caught some interest in the past but with some points been left out. We make a systematic incoherent-light-scattering analysis of the overtone with the use of different gas pressures and polarization orientations for the incident beam. Absolute-scale isotropic and anisotropic spectra are reported along with natural and pressure-induced widths and shifts, and other spectral features such as the peaks corresponding to the (experimentally indistinguishable) interfering channels Eg and F2g hitherto seen solely as two-photon IR-absorption features. We make the first-ever prediction of the SF6 polarizability second derivative with respect to the ν3-mode coordinate and we develop a heuristic argument to explain why the superposition of the three degenerate stretching motions that are related to the ν3 mode cannot but generate a polarized Raman band.